Pak. J. Engg. & Appl. Sci. Vol. 16, Jan., 2015 (p.

1724)

Brine Purification for Chlor-Alkalis Production Based on

Membrane Technology
J R Khan*, Shah Muhammad, Nadeem Feroze, Syed Mustsfa Ali Bukhari. Yasir Khurshid and Abdul Wahab
Malik

Department of Chemical Engineering, University of Engineering and Technology, Lahore Pakistan

*Corresponding author: E-mail:drjrabbani@yahoo.com

Abstract
The experimental work is concerned to process and schematic methodology to reduce the
percentage of sulfates and also to minimize the concentration of other impurities such as Calcium and
Chlorate. The technology used in this study is a unique combination of primary and secondary
treatment of raw brine to prepare a feed for the production of chlor-alkalis.

A series of experimentation was conducted for the determination of major constituents and other
trace metals in the brine using ICP spectrophotometer. The major elements determined were sodium,
calcium, magnesium, potassium, strontium, sulfur and chloride. The trace metals determined were
iron, barium, silicon, nickel, manganese, chromium, copper and boron. The influence of different
parameters like concentration, temperature, pressure, impurity, pH, resin capacity was studied
experimentally. On the basis of data collected and their analysis it can be concluded that best results
are obtained when the treating chemicals Na2CO3, NaOH and Flocculating agent (Anionic) may be
added to brine as a separate addition point.

Key Words: Brine; Purification; Membrane Technology; Chlor-alkalis

1. Introduction of a country, especially in the sector of derived

chemicals, textiles, thermoplastics, polymeric
Many people think of salt as food seasoning,
products etc. Its need has been increasing
found on every dining table. It is that and far more. It
substantially worldwide in last decades and will
is an essential ingredient in the diet of humans,
continue to increase in the coming times.
animals, and plants and is one of the extensively used
food preservative. It is used as an intermediate in the Three processes generally, mercury, diaphragm
chemical industry to produce many other chemicals. and membranes cell electrolysis are employed for the
Its uses are almost without number, it is almost production of chlor-alkalis. Out of these, membrane
involved in all aspects of human activity, In addition, cell electrolysis has received much attention being a
large amounts of salt are consumed by meat and fish modern as well as having overriding economic and
packers, in water softening, road stabilization, ice and environmental advantages [1, 2].Sodium chloride
snow removal, and recovery of bromine from (brine) is the main input and caustic soda, chlorine
seawater. It had also been used as a means of and hydrogen gas are simultaneously produced in the
exchange in earlier times. membrane cell electrolytic process.
2. Historical Background For membrane process, essentially high purity
Brine is the life blood for Chlor-alkali brine is required as the unwanted impurities (Ca+2,
industries. A passable supply of high quality brine on 1
Mg+2 and SO 4 ) deteriorate membrane performance,
a continuous basis is invaluable for plants operation.
therefore, purification of brine, settling, filtration,
The caustic soda (a Chlor-alkali) industry has vital
acidification, de-chlorination are auxiliary processes
importance because its per capita consumption is
for the quality and efficient production of such
normally considered as an indicator of normal growth
alkalis. Chlor-alkali industry is power intensive and

17
Pak. J. Engg. & Appl. Sci. Vol.16, Jan., 2015

is considered as the second largest consumer of Efforts are also made to properly use the waste
electricity [3,4]. products produced from this industry.

Chlor-alkali industry, being red category

3. Scope of Present Work
industry, generate amount of amount of solid and Researchers have been engaged in developing
liquid waste containing a number of contaminants unconventional and innovative processes that are
such as calcium, magnesium, iron, and other metallic inexpensive, yet achieve highest levels of brine
hydroxides depending on the nature, purity and purity. Present research work describes the prediction
source of sodium chloride rock and imparts a number methods of the process performance and presents
of environmental issues [5]. results obtained in Chlor-alkali plant commissioned
recently. The prime objective is to explore the
In the past decades much work is done and technical possibility and economic feasibility to
studies (such as waste filtration and recycling of introduce a simple technique for the purification of
supernatant, using single cell of large size, enhancing raw brine. The purification operation is designed to
cathode and anode reaction by magnetic modification avoid unwanted components (i.e., purification of
of electrodes surfaces and source reduction), are calcium, Barium, Magnesium and other trace
conducted and suggestion are made by researchers to elements). These operations are classified as primary
evaluate the characteristics of effluent as well as to stage includes precipitation, purification, and
identify the prospective waste minimization filtration. Secondary purification unit is comprised of
approaches [6-9]. Studies show that magnetic an ion-exchange membrane circuit to perform high
modified electrode flux is larger than flux of non- quality of separation of impurities like Sr, SiO2,
magnetically modified electrodes [13, 14]. heavy metals. Whereas the 3rd step high temperatures
and high pressure liquefaction systems need
Out of all these approaches, source reduction are cryogenic system to store liquid chlorine is very
usually the lowest cost practical alternate to adopt for expensive and advanced process. The present work is
improving production process. A study show the an effort to bridge the gap for the development of an
maintenance cost is reduced to much extent while economical and efficient method which can be
waste disposal cost is reduced by 55% [15]. applied at chlor-alkali industries.

18
 Hybrid Treatment of Black Liquor to Control Scaling Paper Industry

4. Experimental Setup and 6. Discussion of Results

Experimentation
As is often the case, there is both art and science
The systematic block diagram for the primary at work in making a specific brine treatment system
and secondary refinement of brine solution is given work. Figre-1 reveals the results of order of inputs
in fig 1 and 2.
((Na OH & Na2 CO3) and flocculating agent to
A series of experiments were performed to study remove the suspended particles. It shows that option-
the effects of order and amount of addition of 4 provides the best results. Formation of and settling
chemicals and of various variables on the settling rate rate of contaminants suspended particles (Ca CO3&
and removal of suspended particles. Their graphical Mg (OH)2) and their settling rate depends upon
representation is presented in the subsequent figures. inputs in excess and temperature of brine. It is
The amounts of both major contaminant components observed that excess inputs and higher temperature
and trace metals in the brine were calculated a using reduce the solubility of contaminants and increase the
ICP spectrophotometer DR/4004U. crystal size and settling rate as shown in Figure-2, 3.
The effect of imputes i.e. of magnesium content on
Additionally a Turbiditimeter-2100N and the size of crystals and their settling rate is revealed
inductively coupled plasma optical emition in Figure-4 which shows that the brine with higher
spectrometry were also used to analyze the datas
content will have lower settling rate of contaminates,
5. Order of Inputs thereby resulting into a process difficulty. The effect
of pressure and temperature on the contaminants
1. Addition of all chemicals together.
settling rate and their removal is shown in Figures-5,
2. Separate addition with Na2CO3,ahead of NaOH 6. It is observed that higher pressure and temperature
and flocculating agent. significantly increase the settling rate and removal of
3. Separate addition with NaOH, ahead of Na2CO3 contaminants. Figures-7, 8 expose the effect of PH
and flocculating agent. and temperature on the calcium ions breakthrough.
4. Separate addition with Na2CO3,ahead of NaOH Figure-7 shows that pH in between 8 to 11 favours to
and a separate addition point of flocculating remove the calcium efficiently. However, PH greater
agent than 11.

19
Pak. J. Engg. & Appl. Sci. Vol.16, Jan., 2015

Fig. 1 Order of Chemical Addition vs Suspensoids Removal in Saturated Brine

Fig. 2 Concentration of CaCO3 vs. Na2CO3 in Saturated Brine.

20
 Hybrid Treatment of Black Liquor to Control Scaling Paper Industry

12

Mg(OH)2 (mg/l) 10

6 25C

4 50C
75C
2

0
0 0.02 0.04 0.06 0.08 0.1 0.12

NaOH(gpl)

Fig. 3 Concentration of Mg(OH)2 vs Caustic Concentration in Saturated Brine

Fig. 4 Effect of Mg Impurity on Setting of Particles

Fig. 5 Effect of pressure on Suspensoids Removal in a Vertical Tubular Backwash filter

21
Pak. J. Engg. & Appl. Sci. Vol.16, Jan., 2015

Fig. 6 Effect of Temperature on Suspensoids Removal in a Vertical tubular Backwash Filter

Fig. 7 Effect of Temperature on Suspensoids Removal in a Vertical tubular Backwash Filter

Fig. 8 Effect of Temperature on Calcium Ions Breakthrough

22
 Hybrid Treatment of Black Liquor to Control Scaling Paper Industry

Fig. 9 Effect of Resin Capacity on Calcium Concentration

promote the formation of metal hydroxide 00C-550C as shown in graph # (2 and 3) for
precipitates that are in soluble and may cause efficient settling of impurities and improved
padding of the resin bed and higher pressure drop clarity.
across the column. However, higher temperature of 5. After primary brine treatment, an increase in
brine results in efficient removal of calcium, higher temperature of the brine at about 550C-600C, as
rate and longer service runs are achieved at 60 C. shown in the graph # 6, prior to secondary brine
treatment is found to be beneficial to accomplish
However, the temperature of bine above 75 may
efficient sub-micron filtration. This is because
cause irreversible resin damage. The effect of
higher temperature increases the particle size
calcium concentration on resin performance is shown
thereby increasing the cake thickness which
in Figure-9. It shows that resin performance increase
results into efficient removal of suspended solids.
when the calcium concentration is above 5ppm.
6. Longer service runs can be achieved if the
6. Conclusions temperature of the brine to ion-exchange
1. Best results are obtained when the treating columns as shown in the graph # 7 is maintained
chemicals Na2CO3, NaOH and Flocculating at about 600C-700C. However a further increase
in temperature, as shown in the graph, is
agent (Anionic) are added to brine as a separate
considered to be detrimental for the resin and
addition point.
will result into breakthrough of hardness not
appropriate for membrane cells.
2. An anionic flocculating agent should be used for
brine having alkaline nature. 7. For efficient calcium removal a brine pH of 8-9
should be maintained as shown in the graph #
3. The elimination of magnesium impurity should 8.However, a pH of less than 8 drastically
be of prime concern because the presence of reduces calcium removal capacity. Similarly, as
magnesium impurity results into longer settling shown in the graph # 8, a pH greater than 11
and poor brine quality as shown in graph #4. though has no significant effect on resin
performance but it does promote the formation of
4. The temperature of brine during the addition of metal hydroxide precipitate has low solubility.
treating chemicals should be about These insoluble solids will eventually plug the

23
Pak. J. Engg. & Appl. Sci. Vol.16, Jan., 2015

resin bed, creating an excessive pressure drop [8] Olin Chlor Alkali Products, Becancour, QC,
across the column and thus results into Montreal,Canada, (2003), available at: olin-
breakthrough of hardness not desirable for hloralkali.com /Locations/BecancourQC.aspx
membrane cells. Calcium concentration in brine
should be lowered up to l0ppm prior to entering [9] Das Shantunu, Babu C.S., Kumar Sushil, The
in ion-exchange columns for longer service runs success story of energy saving by design
and efficient calcium removal. modification at chlorine compressor discharge at
chlor-alkali plant,RIL, Dahej, page 2, available
6. References at : energymanage Training.com
/announcement/../Shantunu Das,(2012)
[1] Executive Summary of Integrated Pollution
Prevention and Control (IPPC) in Chlor-Alkali [10] Chloralkali, Grasim India Limited, Chemical
manufacturing industry, European Commission, Division, Nagda, Madhya Pradesh, Major
European IPPC Bureau, December,(2001) Project Implemented for Energy Conservation,
page131, (2008), available at :
[2] OlufemiBabatope A., Ozowe Williams emtindia.net/eca2008/
O.,KomolafeOlolade O., ARPN Journal of Awardbooklet2008/05chlor_Alkali.pdf
Engineering and Applied Sciences, 6(3), pp. 49
(2011). [11] Parikh P.N., Improvement initiatives for chlor-
alkali sector @ PAT scheme of Govt. of India,
[3] OlufemiBabatope, Popoola Grace, Potential assessment from baseline EA, EE
TowobolaOluwatobi and AwosanyaOlanrewaju, Technologies, Waste minimization & Energy
athematicalModelling of a Reduced Thermal Productivity,(2012).
Energy Consuming Spary Dryer for Evaporating
Caustic Soda Solution, Research Journal of [12] Gupta Amit&RajurkarPrashant, Waste
Applied Sciences,Engineering and Technology, Minimisation in a Chlor-Alkali Plant,
4(11), pp. 1550-1556 (2012). Department of Chemical Engineering, Indian
Institute of Technology, Mumbai-400076,India,
[4] Beal, M.G.in Modern Chlor-Alkali 14th July,(2001).
Technology Vol.6, R.W.Curry (editor), The
Royal Chemical Society, Cambridge UK,(1995). [13] Mcketta, J.J. and.Weismantel, G.E (editors)
Encyclopedia of Chemical Processing and
[5] Munoz E, Navia R, Life cycle assessment of Design , Vol.51, pp. 126-188 , Marcel Dekker,
solid waste management strategies in a chlor- New York, 1995.
alkali production facility, Waste Manage. Res.,
29, pp. 634-643(2011). [14] Basu, S., Mukhopadhyay, S.K., Gangopadhyay,
A. and S.G. Dastidar.,Characteristic Change of
[6] Chlor-Alkali Plants, Pollution Prevention and Effluent from a Chlor-alkali Industry of India
Abatement Handbook, World Bank Group due to Process Modification, International
(1998). Research Journal of Environment Sciences, Vol.
2(2), 44-47, February (2013).
[7] Minteer Shelley D, Dittman Mark R., Pasek
Sarah J. and Reidy Shana ; Magnetic Field [15] Unnikrishnan, H., Rakesh, A., Single Stage
Effects on Electrosynthetis Processes, Brine Filtration System in Chlor-Alkali
Department of Chemistry, Saint Louis Industries, International Journal of Engineering
University, 3501, Laclede Ave., St.Louis, MO Trends and Technology (IJETT) Volume 9
63103 (2012). Number 5 - Mar (2014).

24